EP1940741B1 - Procédé économique de fabrication d'une matière de carbonate de calcium finement concassée ensemble du type gcc et pcc, produits ainsi obtenus et leurs utilisations - Google Patents

Procédé économique de fabrication d'une matière de carbonate de calcium finement concassée ensemble du type gcc et pcc, produits ainsi obtenus et leurs utilisations Download PDF

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Publication number
EP1940741B1
EP1940741B1 EP06831537.3A EP06831537A EP1940741B1 EP 1940741 B1 EP1940741 B1 EP 1940741B1 EP 06831537 A EP06831537 A EP 06831537A EP 1940741 B1 EP1940741 B1 EP 1940741B1
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EP
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Prior art keywords
calcium carbonate
gcc
pcc
carbonate material
ground calcium
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EP06831537.3A
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German (de)
English (en)
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EP1940741A1 (fr
Inventor
Christian Rainer
Michael Pohl
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Omya International AG
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Omya International AG
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Priority to EP13005684.9A priority Critical patent/EP2786966A3/fr
Priority to EP06831537.3A priority patent/EP1940741B1/fr
Priority to SI200632313T priority patent/SI1940741T1/sl
Publication of EP1940741A1 publication Critical patent/EP1940741A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/385—Oxides, hydroxides or carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding or treatment with ultrasonic vibrations
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • GCC ground calcium carbonate
  • PCC precipitated calcium carbonate
  • the BET specific surface area is preferably less than 25 m 2 /g.
  • the BET specific surface area is preferably less than 20 m 2 /g, less than 18 m 2 /g, and less than 15 m 2 /g, respectively.
  • Another object of the present invention lies in the co-ground calcium carbonate material (i.e. : aqueous mineral slurries containing the co-ground GCC and PCC and dry products containing the co-ground GCC and PCC) obtained through this process.
  • co-ground calcium carbonate material i.e. : aqueous mineral slurries containing the co-ground GCC and PCC and dry products containing the co-ground GCC and PCC
  • Another object of the present invention lies in the uses of such products in any sector making use of mineral material, and notably in the paper, paint and plastic industries.
  • Clay has traditionally been used for this purpose due to its low cost relative to other mineral pigments.
  • Calcium carbonate (CaCO 3 ) is used as both a coating and filling pigment, and is notably known to improve some of the optical properties of the final product, such as gloss, opacity or brightness.
  • Calcium carbonate can be of two types: ground or natural calcium carbonate referred to as GCC, and synthetic or precipitated calcium carbonate referred to as PCC.
  • Ground calcium carbonate is calcium carbonate obtained from natural sources, such as limestone, marble or chalk, and processed through a treatment such as grinding.
  • Precipitated calcium carbonate is a synthesized material, generally obtained by precipitation following reaction of carbon dioxide and lime in an aqueous environment.
  • This PCC may be rhombohedral and/or scalenohedral and/or aragonitic. According to the needs of the man skilled in the art, this GCC or PCC may additionally be surface treated, for example with stearine.
  • EP 0 894 836 which discloses a slurry consisting of water, commercially available dispersant which prevents the dissociation of agglomerated pigment in the slurry, and agglomerated carbonate-containing pigment with a particle size distribution in which 80-99 % by weight are below 2 ⁇ m in size, 50-90 % by weight are below 1 ⁇ m and 0-10 % by weight are below 0.2 ⁇ m, a steepness factor (ratio of diameter at 50 % by weight to diameter at 20 % by weight) is of 1.5-2.0 and a porosity is of 45-65 %.
  • the proposed solution lies in a process comprising the step of forming a dispersant-free aqueous suspension of natural calcium carbonate, wet-grinding the suspension to produce a calcium carbonate composition having steepness ratio (A) and aging the suspension at temperature below 35°C to produce a calcium carbonate composition having steepness ratio (B) smaller than the ratio (A).
  • the steepness factor is defined as the average diameter of the particles in the 75 % mass divided by the average diameter of the particles in the 25 % mass, when the size distribution is represented using a SedigraphTM.
  • These pigments comprise a first component, which is PCC and a second component which is a processed particulate hydrous kaolin clay having a shape factor of at least 25 and a steepness of at least 20, or a first component, which is a PCC having a spherical particle shape and a second component which is a processed particulate hydrous kaolin clay having a shape factor at least 45, and a mean equivalent particle diameter of less than 0.5 ⁇ m, or a first component which is a PCC and a second component, which is a processed particulate hydrous kaolin clay having a shape factor less than 25.
  • WO 2002 / 016 509 teaches that to improve the optical properties of paper and printability of paper coatings, it is advantageous to use kaolin having a mean particle size of 0.7-3 ⁇ m and a shape factor of at least 60; this type of kaolin can used in combination with another filler such as talc, calcium sulfate and/or alkaline earth metal carbonate.
  • WO 2000 / 066 510 teaches that pigment compositions comprising a blend of a fine kaolin produced from block kaolin clay, and a calcium carbonate which may be either GCC or PCC, wherein both particles have a median particle size less than 0.8 ⁇ m, and a steepness factor, defined as 100 x d 30 /d 70 , greater than 38, and wherein the kaolin / carbonate weight ratio is of 40/60, preferably of 50/50, can improve the optical properties and printability of coated paper.
  • WO 2004 / 016 566 discloses a method for preparing a pigment composition consisting in mixing PCC having a median particle size by weight of less than 1.6 ⁇ m and a GCC having a median particle size by weight of less than 0.8 ⁇ m, in a weight ratio PCC to GCC of 3:2 to 1:9. It does not teach anything about an eventual fraction of fine particles obtained via the process according to the invention. Nevertheless, examples demonstrate clearly that the weight % of particles finer than 1 ⁇ m is largerly lower than 50 %.
  • DE 4 128 570 discloses a carbonate filler and pigment with specified particle shape and size for filling and coating paper, giving high opacity, degree of whiteness and filler content.
  • Such carbonate filler and pigment have rhombohedral or round particle shape, a gradient factor (ratio of particle diameter in ⁇ m at 50 / 20 weight %) of 1.1-1.4, ratio R of % particles finer than 1 ⁇ m / % particles finer than 0.6 ⁇ m ranging from 8 to 19, and average statistic particle diameter ranging from 0.4 to 1.5 ⁇ m.
  • This document also indicates that is possible to obtain a blend of calcium carbonate particles where 70 %, and preferably 95 % by dry weight are finer than 1 ⁇ m.
  • WO 2004 / 059 079 discloses particulate pigment composition, useful in paper, comprising a first pigment which is ground calcium carbonate and a second pigment which is precipitated or ground calcium carbonate, the first and the second pigment having different size distribution steepness factors (100 x d 30 /d 70 ). More precisely, the claimed particulate pigment composition comprises two pigment components. The first comprises particulate GCC carbonate having a steepness factor of 30-45, and the second comprises PCC with a steepness factor of 55-75, and diameter of at most 0.5 ⁇ m, or GCC with a steepness factor of 40-55. Tests n° 10 and 13 carried out by the Applicant disclose a blend of calcium carbonates of both types where 87 % by dry weight of the particles have a mean diameter lower than 1 ⁇ m.
  • This process lies in a process for the preparation of co-ground calcium carbonate material of the GCC and PCC type, presenting a fraction of particles finer than 1 ⁇ m of greater than 80 %, preferably of greater than 85 %, more preferably of greater than 90 %, and even more preferably of greater than 95 %, and a BET specific surface area of less than 25 m 2 /g.
  • the BET specific surface area is preferably less than 25 m 2 /g.
  • the BET specific surface area is preferably less than 20 m 2 /g, less than 18 m 2 /g, and less than 15 m 2 /g, respectively.
  • the invention lies in a process of manufacturing a co-ground calcium carbonate material comprising GCC and PCC, presenting:
  • EP 0 850 880 discloses an aqueous slurry or dehydrated wet cake with a 25-75 % solids concentration comprising a mixture of PCC and a viscosity reducing agent which is dispersed in a mixer to give a slurry with a viscosity below 1000 cp (at 25 °C), and which comprises 0.2-3 ⁇ m median diameter calcium carbonate particles.
  • the slurry is then admixed with 1.5-30 ⁇ m median diameter dry ground calcium carbonate particles to give a weight ratio of to(II) of 20 : 80 to 80 : 20 and a solids concentration of 60-85 %.
  • the slurry is next dispersed in a mixer to a viscosity below 1000 cp and finally dispersed in a sand grinding mill to give a product aqueous slurry comprising 0.2-2 ⁇ m median diameter calcium carbonate particles.
  • This patent also mentions that the obtained calcium carbonate particles have a BET specific surface area in the range of 5 to 25 m 2 /g.
  • the EP 0 850 880 patentee teaches the above process as a solution to counter the high shear rheology difficulties encountered when the GCC component is wet ground, which is a technical problem different than the one solved by the present invention.
  • a first object of the invention consists in a process of manufacturing a co-ground calcium carbonate material comprising GCC and PCC, presenting:
  • the BET specific surface area is preferably less than 25 m 2 /g.
  • the BET specific surface area is preferably less than 20 m 2 /g, less than 18 m 2 /g, and less than 15 m 2 /g, respectively.
  • step (a) the calcium carbonate material is provided as an aqueous suspension, and in that this aqueous suspension contains from 20 to 80 % by dry weight of calcium carbonate, preferably from 50 to 75 %, and most preferably from 50 to 70 %.
  • Said aqueous suspension may result from the dispersion of calcium carbonate material in the form of a wet cake.
  • the wet ground natural calcium carbonate may be subjected to a wet beneficiaation step prior to step (b), allowing the removal of impurities, such as silicate impurities, for instance by froth flotation.
  • impurities such as silicate impurities
  • step (c) is carried out.
  • step (d) is carried out.
  • the process according to the invention is also characterised in that the co-grinding of GCC and PCC during step (b) is conducted in aqueous medium, wherein the concentration of calcium carbonate ranges from 20 to 80 % (by dry weight of calcium carbonate), preferably from 50 to 75 %, and most preferably from 50 to 70 %.
  • the process according to the invention is also characterised in that at least one dispersing and / or grinding aid agent present in a weight % relative to the total dry mineral material ranging from 0 to 2 %, preferably from 0.2 to 1.4 %, and most preferably from 0.5 to 1.2 % may be added before, during or after co-grinding in step (b).
  • Such additives may be added to obtain a stable ProokfieldTM viscosity of less than 3000 mPa.s, preferably of less than1000 mPas, as measured at 25°C.
  • the skilled man in the art will choose the dispersing and / or grinding aid agent as a function of the properties he wishes to achieve. He can use, for instance, homopolymers of (meth)acrylic acid and / or copolymers of (meth)acrylic acid in combination with other water soluble monomers, such homo- and copolymers, which are totally or partially neutralised.
  • the process according to the invention is also characterised in that the co-grinding of GCC and PCC during step (b) is conducted in the presence of at least another mineral material selected from among talc, clay, Al 2 O 3 , TiO 2 or mixtures thereof.
  • the other mineral material is selected among from talc, clay or mixtures thereof.
  • the other mineral material is talc or clay.
  • the process according to the invention is also characterised in that the co-grinding of GCC and PCC during step (b) occurs at a pH of above 7.
  • the process according to the invention is characterised in that the co-grinding of GCC and PCC during step (b) occurs at a pH of above 10.
  • the process according to the invention is characterised in that the co-grinding of GCC and PCC during step (b) occurs at a pH of above 11.
  • This pH increase can be the result of, for example, one or more of the following: by the addition of a base, preferably of a mono or divalent cation, most preferably of sodium or calcium, by the addition of an alkaline preparation of a biocide, or by the release of hydroxide, such a Ca(OH)2, during grinding of a material, such as during the co-grinding of PCC and GCC.
  • a base preferably of a mono or divalent cation, most preferably of sodium or calcium
  • hydroxide such as Ca(OH)2
  • the process according to the invention is also characterised in that the grinder contents are subject to a temperature rise to above 60°C, preferably to above 90°C, and most preferably to above 100°C.
  • This temperature refers to the temperature reached by the mill contents at any one point in the mill.
  • the mill contents at the mill base may be subject to a higher temperature as a result of a higher hydrostatic pressure.
  • the process according to the invention is also characterised in that the PCC present when co-grinding during step (b) accounts for 10 to 90 % of the total combined PCC and GCC weight, preferably from 20 to 80 % of the total combined PCC and GCC weight, and most preferably from 30 to 70 % of the total combined PCC and GCC weight.
  • the process according to the invention is also characterised in that the co-grinding of GCC and PCC during step (b), is conducted in the presence of ceria-containing zirconium oxide grinding beads as grinding media, such beads having:
  • This grain size is determined by analysis of scanning electron microscope images of the beads. Bead ceria content is analysed by ICP Optical Emission Spectrometry.
  • the process according to the invention is also characterised in that the beads have an original diameter prior to grinding of between 0.2 and 1.5 mm, preferably of between 0.4 and 1.0 mm.
  • Another object of the present invention lies in the co-ground calcium carbonate material comprising GCC and PCC, characterised in that it is obtained by the process according to the invention.
  • Another object of the present invention lies in calcium carbonate material comprising GCC and PCC, characterised in that it is in the form of an aqueous suspension, presenting :
  • the BET specific surface area is preferably less than 25 m 2 /g.
  • the BET specific surface area is preferably less than 20 m 2 /g, less than 18 m 2 /g, and less than 15 m 2 /g, respectively.
  • the co-ground calcium carbonate material in the form of an aqueous suspension is also characterised in that it contains 20 to 80 % by dry weight of calcium carbonate material, preferably 40 to 75 % by dry weight of calcium carbonate material, and most preferably 60 to 70 % by dry weight of calcium carbonate material.
  • the co-ground calcium carbonate material in the form of an aqueous suspension is also characterised in that the PCC present accounts for 10 to 90 % of the total combined PCC and GCC weight, preferably from 20 to 80 % of the total combined PCC and GCC weight, and most preferably from 30 to 70 % of the total combined PCC and GCC weight.
  • the co-ground calcium carbonate material comprising GCC and PCC and in the form of an aqueous suspension according to the invention is also characterised in that it presents a steepness factor of at least about 30, preferably of at least about 40, and most preferably of at least about 45.
  • the steepness factor is defined as d 30 / d 70 x 100, where d x is the equivalent spherical diameter relative to which x % by weight of the particles are finer.
  • the co-ground calcium carbonate material comprising GCC and PCC and in the form of an aqueous suspension according to the invention is also characterised in that it features a d 50 from about 0.2 to about 2 ⁇ m, preferably from 0.2 to 0.8 ⁇ m, and most preferably from about 0.25 to about 0.45 ⁇ m.
  • This d 50 is measured using a SedigraphTM 5100.
  • the co-ground calcium carbonate material comprising GCC and PCC and in the form of an aqueous suspension according to the invention is also characterised in that the aqueous suspension contains at least one dispersing and / or grinding aid agent, such dispersing and / or grinding aid agent being present in a weight % relative to the total dry mineral material ranging from 0 to 2 %, preferably from 0.2 to 1.4 %, and most preferably from 0.5 to 1.2 %.
  • the co-ground calcium carbonate material comprising GCC and PCC and in the form of an aqueous suspension according to the invention is also characterised in that the slurry water passed through a 40 ⁇ m sieve contains less than 1000 ppm of ZrO 2 and less than 200 ppm CeO 2 .
  • the co-ground calcium carbonate material comprising GCC and PCC and in the form of an aqueous suspension according to the invention is also characterised in that the slurry water features a ZrO 2 /CeO 2 weight ratio of 4 to 6.5, preferably of 4.6 to 5.7, and most preferably of 5.3.
  • ZrO2 and CeO2 contents are determined by ICP-OES.
  • Another object of the present invention lies in the co-ground calcium carbonate material comprising GCC and PCC, characterised in that it is in the form of a dry product, presenting:
  • the BET specific surface area is preferably less than 25 m 2 /g.
  • the BET specific surface area is preferably less than 20 m 2 /g, less than 18 m 2 /g, and less than 15 m 2 /g, respectively.
  • the co-ground calcium carbonate material comprising GCC and PCC and in the form of a dry product according to the invention is also characterised in that the PCC present accounts for 10 to 90 % of the total combined PCC and GCC weight, preferably from 20 to 80 % of the total combined PCC and GCC weight, and most preferably from 30 to 70 % of the total combined PCC and GCC weight.
  • the co-ground calcium carbonate material comprising GCC and PCC and in the form of a dry product according to the invention is also characterised in that it presents a steepness factor of at least about 30, preferably of at least about 40, and most preferably of at least about 45.
  • the co-ground calcium carbonate material comprising GCC and PCC and in the form of a dry product according to the invention is also characterised in that it features a d 50 from about 0.2 to about 2.0 ⁇ m, preferably from 0.2 to 0.8 ⁇ m, and most preferably from about 0.25 to about 0.45 ⁇ m.
  • the co-ground calcium carbonate material comprising GCC and PCC and in the form of a dry product according to the invention is also characterised in that the it features a ZrO 2 /CeO 2 weight ratio of from 4 to 6.5, preferably of from 4.6 to 5.7, and most preferably of 5.3.
  • Another object of the present invention lies in the uses of the co-ground calcium carbonate material according to the invention, in any sector making use of mineral material, and notably in the paper, paint and plastic industries.
  • Ground calcium carbonate presenting a median diameter of 1.5 ⁇ m was wet-ground at a solids content of 74.5% in the presence of the following additives: 1.51% sodium polyacrylate, in a two-pass process using ceria-comprising zirconium oxide grinding beads featuring a median bead diameter of 0.45 mm, a CeO 2 content of 16 % by weight relative to the total bead weight, and a grain size after sintering of 0.4 ⁇ m.
  • the specific grinding energy required to obtain a final GCC with a fraction of particles less than 1 ⁇ m of 97 % for this material was of 270 kWh/t.
  • ground GCC material featuring a subsequently diluted solids content of 75 % was then added to a standard paper coating formulation made up of the following proportions of components: 100 parts ground GCC material 10.5 parts SBR latex 0.5 parts synthetic thickener 0.2 parts polyvinyl alcohol 0.2 parts optical brightening agent
  • the above coating was adjusted to a final solids content of 68 % and applied on a standard pre-coated wood-free base paper with a grammage of 71 g/m 2 at a coat weight of 10 g/m 2 /side.
  • This coated base paper was then calendered using a supercalender under the following calendering conditions: calender speed of 800 m/min, calender load of 200 kN/cm and a temperature of 105°C.
  • the gloss of the coated paper surface was of 70 % Tappi 75°.
  • a 76 % solids content slurry of ground calcium carbonate presenting a median GCC diameter of 1.4 ⁇ m was ground in the presence of a 51 % solids content PCC slurry with a median PCC diameter of 0.75 ⁇ m.
  • the PCC to GCC weight ratio in the mill was of 50:50.
  • the total solids content of the slurry in the mill was of 61 % and a median diameter of 1.1.
  • the grinder contents were then co-ground in the presence of the following total additives content: 0.95 wt% sodium polyacrylate, using ceria-comprising zirconium oxide grinding beads featuring a median bead diameter of 0.45 mm, a CeO2 content of 16 % by weight relative to the total bead weight, and a grain size after sintering of 0.4 ⁇ m.
  • the specific grinding energy required to obtain a final co-ground GCC with a fraction of particles less than 1 ⁇ m of 97 % for this material was of 200 kWh/t.
  • the above coating was adjusted to a final solids content of 68 % and applied on a standard pre-coated wood-free base paper with a grammage of 71 g/m 2 at a coat weight of 10 g/m 2 /side.
  • This coated base paper was then calendered using a supercalender under the following calendering conditions: calender speed of 800 m/min, calender load of 200 kN/cm and a temperature of 105°C.
  • the gloss of the coated paper surface was of 72 % Tappi 75°.
  • Example 1 Fraction of particles finer than 1 ⁇ m in the final ground product 97% 97% BET specific surface area of the final ground product 28 g/m 2 23 g/m 2 Steepness factor of the final ground product 35 42 Median diameter of the final ground product 0.27 ⁇ m 0.27 ⁇ m Total specific grinding energy required to produce the product 270 kWh/t 200 kWh/t Tappi gloss of paper coated with a formulation comprising the product 70% 72% Brightness of paper coated with a formulation comprising the product 95.1 % 96.5 % Opacity of paper coated with a formulation comprising the product 89.7 % 90.2 %
  • Table 1 illustrates that the process according to the invention requires less grinding energy to obtain the desired fraction of particles finer than a given value, which leads to an equal/improved gloss, relative to a process of the prior art.
  • Example 4 Example according to the invention.
  • This example illustrates a co-ground PCC and GCC obtained by a process according to the invention.
  • a 74 % solids content slurry of ground calcium carbonate presenting the characteristics listed under Example 4 in Table 2 was ground in the presence of a 48 % solids content PCC slurry with the characteristics listed under Example 4 in Table 2 in a media mill.
  • the PCC to GCC weight ratio in the mill was of 30:70 and the solids content of 65.9 %.
  • the grinder contents were co-ground using yttrium-stabilised zirconium silicate grinding beads featuring a bead diameter prior to grinding of 0.6 to 1.0 mm.
  • a total of 116 kWh/t specific grinding energy was expended in order to obtain a GCC/PCC co-ground end material having the end material characteristics indicated in Table 2.
  • the final solids content of this GCC slurry was of 70.3 %.
  • the above coating was adjusted to a final solids content of 68 % and applied on a standard pre-coated wood-free base paper with a grammage of 71 g/m 2 at a coat weight of 10 g/m 2 /side.
  • This coated base paper was then calendered using a supercalender under the following calendering conditions: calender speed of 800 m/min, calender load of 200 kN/cm and a temperature of 105°C.
  • Table 2 indicates that the process to prepare a co-ground PCC/GCC material according to the invention requires less grinding energy as compared to that required to prepare a comparable blend of PCC and GCC, without any loss or with an improvement in optical properties.
  • This example illustrates the use of a process according to the invention wherein 3 minerals, a natural calcium carbonate a precipitated calcium carbonate and a clay, are co-ground with the use of ceria-containing zirconium oxide grinding beads with a ceria content of 16 % by weight relative to the total weight of said bead, an average grain size after sintering of the grains forming said bead of 0.4 ⁇ m and a median bead diameter of 0,45 mm.
  • the co-ground material is then added to a coating formulation used to coat a base paper, and the resulting gloss is measured.
  • the weight ratio PCC:GCC:clay in the mill was of 45:45:10.
  • the total solids content of the slurry in the mill was of 72 % and the median diameter was of 0.4 and 0.5 ⁇ m for the 2 tests illustrating the invention.
  • the grinder contents were then co-ground in the presence of the following total additives content:
  • the 2 obtained slurry of the co-processed material was then added to a standard paper coating formulation made up of the following weight proportions of components : 100 parts co-processed material 11 parts SBR latex (DL 966 commercialized by DOW CHEMICALSTM) 0.5 parts synthetic thickener (CMC FF5 commercialized by FINNFIXTM ) 0.4 parts polyvinyl alcohol (PVA 4-98 commercialized by CLARIANT TM ) 0.6 parts optical brightening agent (BlancophorTM P commercialized by BAYERTM)
  • the above coating was applied on a standard topcoat base paper with a grammage of 78 g/m 2 at a coat weight of 10 g/m 2 /side.
  • This coated base paper was then calendered using a supercalender under the following calendering conditions: calender speed of 300 m/min, calender load of 170 kN/m and a temperature of 80 °C.
  • the gloss of the coated paper surface was of 73 % Tappi 75 deg. and 45 % DIN 75 deg..
  • the same coating manufactured with 100 parts of a GCC having a median diameter of 0.4 ⁇ m was of 70 % Tappi 75 deg. and 35 % DIN 75 deg..
  • the gloss of the coated paper surface was of 68 % Tappi 75 ° and 40 % DIN 75 °.
  • the same coating manufactured with 100 parts of a GCC having a median diameter of 0.4 ⁇ m was of 63 % Tappi 75 ° and 33 % DIN 75 °.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Paper (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Medicinal Preparation (AREA)

Claims (43)

  1. Procédé de fabrication d'une matière de carbonate de calcium concassée ensemble comprenant du GCC et du PCC, présentant :
    - une fraction de particules plus fines que 1 µm supérieure à 80 %, de préférence supérieure à 85 %, plus préférablement supérieure à 90 %, et encore plus préférablement supérieure à 95 %, et
    - une surface spécifique BET inférieure à 25 m2/g
    et caractérisé en ce qu'il comprend les étapes de :
    (a) production de GCC sous la forme d'une suspension aqueuse,
    (b) concassage ensemble de GCC et de PCC, éventuellement avec au moins une autre matière minérale, jusqu'à ce que la fraction de particules plus fines que 1 µm soit supérieure à 80 %, de préférence supérieure à 85 %, plus préférablement supérieure à 90 %, et encore plus préférablement supérieure à 95 % ; et jusqu'à ce que la surface spécifique BET soit inférieure à 25 m2/g,
    (c) criblage et/ou augmentation de concentration éventuels de la matière de carbonate de calcium concassée ensemble obtenue suite à l'étape (b),
    (d) séchage éventuel de la matière de carbonate de calcium concassée ensemble obtenue suite à l'étape (b) ou (c).
  2. Procédé selon la revendication 1, caractérisé en ce que pour une fraction de particules plus fines que 1 µm supérieure à 95 %, la surface spécifique BET est inférieure à 25 m2/g.
  3. Procédé selon la revendication 1, caractérisé en ce que pour une fraction de particules plus fines que 1 µm supérieure à 90 %, la surface spécifique BET est inférieure à 20 m2/g.
  4. Procédé selon la revendication 1, caractérisé en ce que pour une fraction de particules plus fines que 1 µm supérieure à 85 %, la surface spécifique BET est inférieure à 18 m2/g.
  5. Procédé selon la revendication 1, caractérisé en ce que pour une fraction de particules plus fines que 1 µm supérieure à 80 %, la surface spécifique BET est inférieure à 15 m2/g.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que dans l'étape (a), la matière de carbonate de calcium est produite sous la forme d'une suspension aqueuse, et que cette suspension aqueuse présente une teneur en solides allant de 20 à 80 %, de préférence de 50 à 75 %, et idéalement de 50 à 70 %.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'étape (c) est effectuée.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que l'étape (d) est effectuée.
  9. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le concassage ensemble du GCC et du PCC pendant l'étape (b) est effectué en milieu aqueux, dans lequel la concentration de carbonate de calcium va de 20 à 80 % (par poids sec de carbonate de calcium), de préférence de 50 à 75 %, et plus préférablement de 50 à 70 %.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que ledit au moins un adjuvant de dispersion et/ou de concassage présent dans un % massique par rapport à la matière minérale sèche totale allant de 0 à 2 %, plus préférablement de 0,2 à 1,4 %, et idéalement de 0,5 à 1,2 %, est ajouté avant, pendant ou après l'étape (b).
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que le concassage ensemble du GCC et du PCC pendant l'étape (b) est effectué en présence d'au moins une autre matière minérale choisie parmi le talc, l'argile, Al2O3, TiO2 ou des mélanges de ceux-ci.
  12. Procédé selon la revendication 11, caractérisé en ce que le concassage ensemble du GCC et du PCC pendant l'étape (b) est effectué en présence d'au moins une autre matière minérale choisie parmi le talc, l'argile ou des mélanges de ceux-ci.
  13. Procédé selon la revendication 12, caractérisé en ce que le concassage ensemble du GCC et du PCC pendant l'étape (b) est effectué en présence de talc.
  14. Procédé selon la revendication 12, caractérisé en ce que le concassage ensemble du GCC et du PCC pendant l'étape (b) est effectué en présence d'argile.
  15. Procédé selon l'une quelconque des revendications 1 à 14, caractérisé en ce que le concassage ensemble du GCC et du PCC pendant l'étape (b) se produit à un pH supérieur à 7.
  16. Procédé selon la revendication 15, caractérisé en ce que le concassage ensemble du GCC et du PCC pendant l'étape (b) se produit à un pH supérieur à 10.
  17. Procédé selon la revendication 16, caractérisé en ce que le concassage ensemble du GCC et du PCC pendant l'étape (b) se produit à un pH supérieur à 11.
  18. Procédé selon l'une quelconque des revendications 1 à 17, caractérisé en ce que pendant le concassage ensemble du GCC et du PCC dans l'étape (b), le contenu du concasseur est soumis à une hausse de température supérieure à 60°C, de préférence supérieure à 90°C, et idéalement supérieure à 100°C.
  19. Procédé selon l'une quelconque des revendications 1 à 18, caractérisé en ce que la fraction massique du PCC par rapport au poids total du GCC et du PCC va de 10 à 90 %, de préférence de 20 à 80 %, et idéalement de 30 à 70 %.
  20. Procédé selon l'une quelconque des revendications 1 à 19, caractérisé en ce que le concassage ensemble du GCC et du PCC pendant l'étape (b), est effectué en présence de billes de concassage d'oxyde de zirconium contenant de l'oxyde de cérium comme milieu de concassage, ces billes présentant :
    - une teneur en oxyde de cérium comprise entre 14 et 20 % en poids par rapport au poids total desdites billes, de préférence compris entre 15 et 18 % en poids par rapport au poids total desdites billes, et idéalement d'environ 16 % en poids par rapport au poids total desdites billes ; et
    - une taille moyenne de grain après frittage des grains formant lesdites billes inférieure à 1 µm, de préférence inférieure à 0,5 µm, et idéalement inférieure à 0,3 µm.
  21. Procédé selon la revendication 20, caractérisé en ce que les billes ont un diamètre original avant concassage compris entre 0,2 et 1,5 mm, de préférence compris entre 0,4 et 1,0 mm.
  22. Matière de carbonate de calcium concassée ensemble comprenant du GCC et du PCC, caractérisée en ce qu'elle est sous la forme d'une suspension aqueuse, présentant :
    - une fraction de particules plus fines que 1 µm supérieure à 80 %, de préférence supérieure à 85 %, plus préférablement supérieure à 90 %, et encore plus préférablement supérieure à 95 %, et
    - une surface spécifique BET inférieure à 25 m2/g.
  23. Matière de carbonate de calcium concassée ensemble selon la revendication 22, caractérisée en ce que pour une fraction de particules plus fines que 1 µm supérieure à 95 %, la surface spécifique BET est inférieure à 25 m2/g.
  24. Matière de carbonate de calcium concassée ensemble selon la revendication 22, caractérisée en ce que pour une fraction de particules plus fines que 1 µm supérieure à 90 %, la surface spécifique BET est inférieure à 20 m2/g.
  25. Matière de carbonate de calcium concassée ensemble selon la revendication 22, caractérisée en ce que pour une fraction de particules plus fines que 1 µm supérieure à 85 %, la surface spécifique BET est inférieure à 18 m2/g.
  26. Matière de carbonate de calcium concassée ensemble selon la revendication 22, caractérisée en ce que pour une fraction de particules plus fines que 1 µm supérieure à 80 %, la surface spécifique BET est inférieure à 15 m2/g.
  27. Matière de carbonate de calcium concassée ensemble selon l'une quelconque des revendications 22 à 26, caractérisée en ce qu'elle contient de 20 à 80 % par poids sec de matière de carbonate de calcium, de préférence de 40 à 75 % par poids sec de matière de carbonate de calcium, et idéalement de 60 à 70 % par poids sec de matière de carbonate de calcium.
  28. Matière de carbonate de calcium concassée ensemble selon l'une quelconque des revendications 22 ou 27, caractérisée en ce que la fraction massique du PCC par rapport au poids total du GCC et du PCC va de 10 à 90 %, de préférence de 20 à 80 %, et idéalement de 30 à 70 %.
  29. Matière de carbonate de calcium concassée ensemble selon l'une quelconque des revendications 22 à 28, caractérisée en ce qu'elle présente un facteur de pente, défini comme étant d30/d70 x 100, supérieur ou égal à environ 30, de préférence supérieur ou égal à environ 40, et idéalement supérieur ou égal à environ 45.
  30. Matière de carbonate de calcium concassée ensemble selon l'une quelconque des revendications 22 à 29, caractérisée en ce qu'elle présente un d50 d'environ 0,2 à environ 2,0 µm, de préférence de 0,2 à 0,8 µm, et de préférence d'environ 0,25 à environ 0,45 µm.
  31. Matière de carbonate de calcium concassée ensemble selon l'une quelconque des revendications 22 à 30, caractérisée en ce que la suspension aqueuse contient au moins un adjuvant de dispersion et/ou de concassage, cet adjuvant de dispersion et/ou de concassage étant présent dans un % massique par rapport à la matière minérale sèche totale allant de 0 à 2 %, plus préférablement de 0,2 à 1,4 %, et idéalement de 0,5 à 1,2 %.
  32. Matière de carbonate de calcium concassée ensemble selon l'une quelconque des revendications 22 à 31, caractérisée en ce que l'eau de suspension ayant traversé un tamis à 40 µm contient moins de 1000 ppm de ZrO2 et moins de 200 ppm CeO2.
  33. Matière de carbonate de calcium concassée ensemble selon l'une quelconque des revendications 22 à 32, caractérisé en ce que l'eau de suspension présente un rapport massique ZrO2/CeO2 de 4 à 6,5, de préférence de 4,6 à 5,7, et idéalement de 5,3.
  34. Matière de carbonate de calcium concassée ensemble comprenant du GCC et du PCC, caractérisée en ce qu'elle est sous la forme d'un produit sec, présentant :
    - une fraction de particules plus fines que 1 µm supérieure à 80 %, de préférence supérieure à 85 %, plus préférablement supérieure à 90 %, et encore plus préférablement supérieure à 95 %, et
    - une surface spécifique BET inférieure à 25 m2/g.
  35. Matière de carbonate de calcium concassée ensemble selon la revendication 34, caractérisée en ce que pour une fraction de particules plus fines que 1 µm supérieure à 95 %, la surface spécifique BET est inférieure à 25 m2/g.
  36. Matière de carbonate de calcium concassée ensemble selon la revendication 34, caractérisée en ce que pour une fraction de particules plus fines que 1 µm supérieure à 90 %, la surface spécifique BET est inférieure à 20 m2/g.
  37. Matière de carbonate de calcium concassée ensemble selon la revendication 34, caractérisée en ce que pour une fraction de particules plus fines que 1 µm supérieure à 85 %, la surface spécifique BET est inférieure à 18 m2/g.
  38. Matière de carbonate de calcium concassée ensemble selon la revendication 34, caractérisée en ce que pour une fraction de particules plus fines que 1 µm supérieure à 80 %, la surface spécifique BET est inférieure à 15 m2/g.
  39. Matière de carbonate de calcium concassée ensemble selon l'une quelconque des revendications 34 à 38, caractérisée en ce que la fraction massique du PCC par rapport au poids total du GCC et du PCC va de 10 à 90 %, de préférence de 20 à 80 %, et idéalement de 30 à 70 %.
  40. Matière de carbonate de calcium concassée ensemble selon l'une quelconque des revendications 34 ou 39, caractérisée en ce qu'elle présente un facteur de pente, défini comme étant d30/d70 x 100, supérieur ou égal à environ 30, de préférence supérieur ou égal à environ 40, et idéalement supérieur ou égal à environ 45.
  41. Matière de carbonate de calcium concassée ensemble selon l'une quelconque des revendications 34 ou 40, caractérisée en ce qu'elle présente un d50 d'environ 0,2 à environ 2,0 µm, de préférence de 0,2 à 0,8 µm, de préférence d'environ 0,25 à environ 0,45 µm.
  42. Matière de carbonate de calcium concassée ensemble selon l'une quelconque des revendications 34 à 41, caractérisée en ce qu'elle présente un rapport massique ZrO2/CeO2 de 4 à 6,5, de préférence de 4,6 à 5,7, et idéalement de 5,3.
  43. Utilisation d'une matière de carbonate de calcium concassée ensemble comprenant du GCC et du PCC selon l'une quelconque des revendications 21 à 42 dans un papier, et en particulier dans des revêtements de papier, dans des peintures et dans des plastiques.
EP06831537.3A 2005-09-16 2006-09-12 Procédé économique de fabrication d'une matière de carbonate de calcium finement concassée ensemble du type gcc et pcc, produits ainsi obtenus et leurs utilisations Active EP1940741B1 (fr)

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EP13005684.9A EP2786966A3 (fr) 2005-09-16 2006-09-12 Procédé de fabrication d'une matière de carbonate de calcium finement concassée du type GCC et PCC, produits ainsi obtenus et leurs utilisations
EP06831537.3A EP1940741B1 (fr) 2005-09-16 2006-09-12 Procédé économique de fabrication d'une matière de carbonate de calcium finement concassée ensemble du type gcc et pcc, produits ainsi obtenus et leurs utilisations
SI200632313T SI1940741T1 (sl) 2005-09-16 2006-09-12 Ekonomičen postopek za proizvodnjo zelo finega sočasno mletega materiala kalcijevega karbonata vrste GCC in PCC, pridobljeni proizvodi in njihove uporabe

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EP05077111A EP1764345A1 (fr) 2005-09-16 2005-09-16 Procédé de fabrication d'une composition de carbonate de calcium fine par co-broyage de GCC et PCC, compositions produites et leurs applications
EP06831537.3A EP1940741B1 (fr) 2005-09-16 2006-09-12 Procédé économique de fabrication d'une matière de carbonate de calcium finement concassée ensemble du type gcc et pcc, produits ainsi obtenus et leurs utilisations
PCT/IB2006/002649 WO2007031869A1 (fr) 2005-09-16 2006-09-12 Procede economique de fabrication d'une matiere de carbonate de calcium finement concassee ensemble du type gcc et pcc, produits ainsi obtenus et leurs utilisations

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EP1764345A1 (fr) 2007-03-21
RU2008114843A (ru) 2009-10-27
US20080308010A1 (en) 2008-12-18
NO20081694L (no) 2008-06-13
TW200724491A (en) 2007-07-01
MA29918B1 (fr) 2008-11-03
TR201901025T4 (tr) 2019-02-21
EP1940741A1 (fr) 2008-07-09
KR20080047472A (ko) 2008-05-28
TWI520907B (zh) 2016-02-11
TNSN08116A1 (en) 2009-07-14
UA96927C2 (uk) 2011-12-26
ES2706545T3 (es) 2019-03-29
SI1940741T1 (sl) 2019-02-28
AU2006290427B2 (en) 2013-06-13
IL190192A0 (en) 2008-11-03
EP2786966A3 (fr) 2014-12-03
JP2009508792A (ja) 2009-03-05
CA2622799A1 (fr) 2007-03-22
CN101282909A (zh) 2008-10-08
KR101307946B1 (ko) 2013-09-13
IL190192A (en) 2016-10-31
CN101282909B (zh) 2013-01-23
BRPI0615945A2 (pt) 2011-05-31
AU2006290427A1 (en) 2007-03-22
RU2438979C2 (ru) 2012-01-10
EP2786966A2 (fr) 2014-10-08
WO2007031869A1 (fr) 2007-03-22
ZA200803224B (en) 2010-02-24
NZ566942A (en) 2011-04-29
CA2622799C (fr) 2012-11-13

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